CN110003380B - Photosensitive resin preparation, forming and driving method for 4D printing - Google Patents

Photosensitive resin preparation, forming and driving method for 4D printing Download PDF

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CN110003380B
CN110003380B CN201910207045.9A CN201910207045A CN110003380B CN 110003380 B CN110003380 B CN 110003380B CN 201910207045 A CN201910207045 A CN 201910207045A CN 110003380 B CN110003380 B CN 110003380B
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photosensitive resin
printing
forming
molded article
shape
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CN110003380A (en
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闫春泽
伍宏志
蔡超
陈鹏
史玉升
杨磊
李昭青
刘主峰
张策
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Huazhong University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B29C64/129—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask
    • B29C64/135—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask the energy source being concentrated, e.g. scanning lasers or focused light sources
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/35—Cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/379—Handling of additively manufactured objects, e.g. using robots
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate

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Abstract

The invention belongs to the field of polymer 4D printing, and discloses a photosensitive resin preparation, forming and driving method for 4D printing. The preparation method comprises the steps of S11, firstly, adding a multifunctional acrylate cross-linking agent into a monofunctional acrylate monomer, and then adding a photoinitiator to obtain a mixture; s12, the mixture is subjected to ultrasonic treatment until colorless and transparent liquid is formed, and photosensitive resin which can be printed by SLA or DLP technology is obtained. The invention also provides a method for forming and driving the corresponding photosensitive resin. The invention adopts the free radical type photosensitive resin system to improve the photocuring rate, the photosensitive resin obtained by adopting the acrylate system containing single functionality and multiple functionality is suitable for SLA or DLP technical forming, the formed piece contains hard segments and soft segments in SMP, and the formed piece shows good shape memory performance, and the thermosetting network formed by the method also has excellent thermal property and mechanical property.

Description

Photosensitive resin preparation, forming and driving method for 4D printing
Technical Field
The invention belongs to the technical field of polymer 4D printing, and particularly relates to a photosensitive resin preparation, forming and driving method for 4D printing.
Background
The intelligent material is a novel functional material which can sense external stimulation, can judge and autonomously change the structure and the function of the intelligent material, and has a sensing function, a feedback function, a response function and a driving function. When the smart material is applied to additive manufacturing, namely, 3D printing technology, a new dimension of "time" is introduced for 3D printing, namely, the so-called just-emerging 4D printing technology. The 3D printed forming part of the smart material can change its shape, performance or function by itself with the passage of time under external stimuli (such as temperature, light, electric field, magnetic field and humidity), which is a very subversive manufacturing technology. The 4D printed product is no longer static but can be dynamically changed. The 4D printing technology changes the traditional motor driving and mechanical transmission mode, does not need complex electromechanical equipment and transmission devices, and can realize the driving and deformation which are needed by people only by applying external stimulation. The 4D printing technology is a product formed by combining the 3D printing technology and the intelligent material, and the product inevitably has the advantages of the 3D printing technology and the intelligent material at the same time, so that the manufacture of a complex structure with low cost, high efficiency and intellectualization is realized, and the deep research on the 4D printing has important theoretical and practical significance for promoting the development of the 3D printing technology and the intelligent material.
At present, the research and development of intelligent materials for 4D printing becomes a hot spot of 4D printing technology research. Shape Memory Polymer (SMP), which is a representative stimulus-responsive Polymer, is one of smart materials, and can return from a temporary Shape to an initial Shape under the external stimulus, and its specific principle of Shape return is as follows: the shaped SMP is raised to a Glass Transition Temperature (Tg) or above, at the moment, the movement of the molecular chain in the polymer is more active, and the material is in a high elastic state which is easy to deform; applying external force within the elastic limit to deform the SMP to obtain a temporary shape, then keeping the external force to reduce the temperature to be below Tg, wherein the SMP is in a glassy state, the movement of molecular chains is frozen, and the deformation is macroscopically shown to be fixed; when the temperature rises above Tg again, the deformation reverts as if the SMP remembers the original shape, as the molecular chains are reactivated. In the prior art, SMP techniques for Fused Deposition Modeling (FDM) are provided, which are thermoplastic polymer strands with lower properties (thermal, mechanical, shape memory) in all respects compared to thermoset SMPs.
Therefore, development of a thermosetting SMP with excellent performance becomes an important development trend of an intelligent material, and forming a shape memory photosensitive resin by using an ultraviolet light curing technology (SLA) is an important means for preparing the thermosetting SMP. The prior art provides an epoxy resin material with a low-temperature shape memory effect, a composition and a preparation method thereof, which realize the adjustment of the thermal response temperature of the material at low temperature (-12-20 ℃). However, the photosensitive resin of the epoxy resin system is a cationic curing system, and the curing rate is low compared to a radical curing system. Therefore, the SMP which has the advantages of high curing speed, good thermal property, mechanical property and shape memory property and can be suitable for the photocuring technology has important significance.
Disclosure of Invention
Aiming at the defects or the improvement requirements of the prior art, the photosensitive resin preparation, forming and driving method for 4D printing is provided, the photosensitive resin system is adopted, the photocuring speed is improved, the photosensitive resin prepared by the acrylate system containing both monofunctional degree and polyfunctional degree is adopted, and the cross-linked structure obtained after photocuring contains the hard segment and the soft segment which are common in shape memory polymers, so that the formed thermosetting network has excellent thermal property, mechanical property and shape memory property.
To achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a photosensitive resin for 4D printing, comprising the steps of:
s11, adding a multifunctional acrylate cross-linking agent into a monofunctional acrylate monomer, and then adding a photoinitiator to obtain a mixture;
s12 subjecting the mixture to ultrasonic treatment until a colorless transparent liquid is formed, to obtain a photosensitive resin useful for 4D printing.
Further, in step S11, the mass fraction ratio of the monofunctional acrylate monomer to the polyfunctional acrylate crosslinking agent is 1: 1-9: 1, the mass of the photoinitiator is 0.5-2% of the total mass of the monofunctional acrylate monomer and the multifunctional acrylate crosslinking agent;
preferably, the mass fraction ratio of the monofunctional acrylate monomer to the multifunctional acrylate crosslinking agent is 3: 1-7: 1, wherein the mass of the photoinitiator is 1-1.5% of the total mass of the monofunctional acrylate monomer and the multifunctional acrylate crosslinking agent.
Further, in step S11, the monofunctional acrylate monomer is any one or more of tert-butyl acrylate, beta-hydroxyethyl acrylate, and isobornyl acrylate; the multifunctional acrylate is any one or more of 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, polyethylene glycol diacrylate and polyethylene glycol dimethacrylate;
the photoinitiator is a free radical type photoinitiator, preferably, the free radical type photoinitiator is any one or more of bis (2,4, 6-trimethylbenzoyl) phosphine oxide, bis (2, 6-dimethoxybenzoyl) - (4',4' -dimethyloctyl-2) phosphine oxide, alpha-diethoxyacetophenone and alpha, alpha-dimethoxy-alpha-phenylacetophenone.
Further, the time of ultrasonic treatment is 5 min-10 min.
According to another aspect of the present invention, there is provided a method of forming a photosensitive resin molded article having a shape memory function, comprising the steps of:
s21, printing and forming the photosensitive resin by adopting a photocuring 3D printing device to obtain a formed piece, and cleaning the residual photosensitive resin on the surface of the formed piece;
s22, the formed piece is irradiated by ultraviolet light to completely solidify the formed piece, and then the photosensitive resin formed piece with the shape memory function is obtained.
Further, in step S21, the photo-curing 3D printing device is an ultraviolet curing device or a digital light processing device; wherein the content of the first and second substances,
the laser scanning speed of the ultraviolet curing equipment is 500-1000 mm/s; the digital light processing equipment carries out layered curing on the photosensitive resin, the thickness of each layer of curing is 20-100 mu m, and the curing time of each layer is 4-8 s.
Further, in step S21, cleaning the photosensitive resin remaining on the surface of the formed part by an alcohol soaking method, wherein the alcohol soaking time is 3min to 5 min;
in step S22, the wavelength of the ultraviolet light is within the wavelength range of the light that can be sensed by the photoinitiator, and the irradiation time of the ultraviolet light is 15min to 20 min.
According to another aspect of the present invention, there is provided a method of driving a photosensitive resin molded article, comprising the steps of:
s31, increasing the temperature of the photosensitive resin forming piece in the initial shape to T1, wherein T1 is larger than the glass transition temperature Tg of the photosensitive resin forming piece, and applying external force to the photosensitive resin forming piece in the initial shape to deform the photosensitive resin forming piece in the initial shape to obtain a temporary-shaped photosensitive resin forming piece;
s32, keeping the applied external force unchanged, lowering the temperature of the temporary shaped photosensitive resin molded article to T2, wherein T2 is less than the glass transition temperature Tg of the photosensitive resin molded article, fixing the temporary shaped photosensitive resin molded article, and removing the external force;
s33 raises the temperature to T1 again, returning the temporarily shaped photosensitive resin molded article to the original shape.
Further, the temperature is raised in the step S31 and the step S33 by a water bath method, and the temperature is lowered in the step S32 by a water bath method; preferably, T1 is Tg +10 ℃ to Tg +30 ℃ and T2 is Tg-10 ℃ to Tg-30 ℃.
Further, in step S31, the external force is within an elastic limit of the photosensitive resin molded article.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) the invention adopts the free radical type photosensitive resin system to improve the photocuring rate and further improve the processing efficiency, adopts the acrylate system containing both single functionality and multiple functionality, and the cross-linking structure obtained by photocuring and forming contains the hard segment and the soft segment which are common in the photosensitive resin system, thereby reflecting good shape memory performance, and the thermosetting network formed by the method also has excellent thermal property and mechanical property.
(2) The invention can adopt photosensitive resin of various acrylate systems, greatly enriches materials for 4D printing, and the glass transition temperature of the SMP formed by 4D printing can be adjusted by adjusting the mass fraction of the cross-linking agent in the photosensitive resin, and the obtained SMP formed by 4D printing has excellent shape fixing rate and shape recovery rate so as to adapt to the requirements of different working temperatures.
(3) The invention adopts a typical 3D printing technology, namely ultraviolet curing equipment or digital light processing equipment to form photosensitive resin, and enables the obtained resin forming piece to have a shape memory effect, thereby successfully realizing 4D printing, and being capable of integrally manufacturing parts with complex structures without a die. Compared with the traditional manufacturing method, the method has the advantage of short design and manufacturing period.
(4) According to the invention, the photocuring forming piece of the photosensitive resin is driven by heating and cooling treatment according to the glass transition temperature of the photosensitive resin, so that the excellent shape fixing rate and shape recovery rate of the forming piece are shown, and the performance requirement of the consumable material for 4D printing is better met.
Drawings
FIG. 1 is a flow chart of a photosensitive resin preparation, forming and driving method for 4D printing according to the present invention;
FIG. 2 is a schematic representation of the preparation, shaping, and formation of a thermoset cross-linked network of photosensitive resin according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of a deformation-drive-recovery process for forming a shaped piece having an initial shape that is a torus and a temporary shape that is an elongated strip, constructed in accordance with an embodiment of the present invention;
FIG. 4 is a schematic view showing a deformation-drive-recovery process of a photosensitive resin 4D printed molded article constructed according to example 1 of the present invention;
FIG. 5 is a graph showing the change of the shape fixation rate with the cycle number of the molded article having different contents of the crosslinking agent in the photosensitive resin system of example 1;
FIG. 6 is a graph showing the change of the shape recovery rate with cycle number of molded articles having different contents of the crosslinking agent in the photosensitive resin system of example 1;
FIG. 7 is a graph showing the relationship between the content of the crosslinking agent and the time required for the shape recovery process in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
As shown in figures 1 and 2, in the invention, monofunctional acrylate is selected as a monomer, multifunctional acrylate is selected as a cross-linking agent, and a photoinitiator is in a free radical type and can sense ultraviolet light in a corresponding waveband. 0.5g to 2g of photoinitiator are added per 100g of the mixture of monomer and crosslinker. Slowly pouring the cross-linking agent with high viscosity into the monomer with relatively low viscosity, adding photoinitiator powder, and performing ultrasonic treatment on the mixture of the cross-linking agent with high viscosity and the monomer with relatively low viscosity to obtain the photosensitive resin with uniform components.
Wherein the mass fraction ratio of the monofunctional acrylate monomer to the multifunctional acrylate crosslinking agent is 1: 1-9: 1, the mass of the photoinitiator is 0.5-2% of the total mass of the monofunctional acrylate monomer and the multifunctional acrylate crosslinking agent. The monofunctional acrylate monomer is any one or more of tert-butyl acrylate, beta-hydroxyethyl acrylate and isobornyl acrylate; the multifunctional acrylate is any one or more of 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, polyethylene glycol diacrylate and polyethylene glycol dimethacrylate.
The photoinitiator is a free radical type photoinitiator, preferably, the free radical type photoinitiator is one or more of bis (2,4, 6-trimethylbenzoyl) phosphine oxide, bis (2, 6-dimethoxybenzoyl) - (4',4' -dimethyloctyl-2) phosphine oxide, alpha-diethoxyacetophenone and alpha, alpha-dimethoxy-alpha-phenylacetophenone.
In a preferred embodiment of the present invention, the mass fraction ratio of the monofunctional acrylate monomer to the polyfunctional acrylate crosslinking agent is 3: 1-7: 1, wherein the mass of the photoinitiator is 1-1.5% of the total mass of the monofunctional acrylate monomer and the multifunctional acrylate crosslinking agent.
As shown in fig. 1 and 2, the present invention further provides a method for preparing the photosensitive resin, wherein a multifunctional acrylate crosslinking agent is added to the monofunctional acrylate monomer, and then a photoinitiator is added, and the mixture is uniformly mixed and subjected to ultrasonic treatment to obtain the photosensitive resin. Wherein the time of ultrasonic treatment is preferably 5min to 10 min.
The invention also provides a method for forming a photosensitive resin formed part with a memory function, which comprises the steps of firstly, slowly pouring the prepared resin into a resin tank of a light curing device, introducing a three-dimensional CAD model into the device to form the resin, and soaking the formed part with alcohol after forming to clean the residual resin on the surface of the formed part; and then, the formed part is further illuminated in the ultraviolet curing lamp box, so that the uncured resin in the formed part is more fully and completely cured, and the cured resin can be taken out from the ultraviolet curing lamp box. Wherein the light curing device adopts SLA (namely ultraviolet light curing device) or DLP device (namely digital light processing device), and the wave band of the light which can be sensed by the adopted photoinitiator contains the wavelength of the ultraviolet light in the SLA or DLP device. When SLA equipment is used, the scanning speed of the laser is 500-1000 mm/s; when using a DLP device, the thickness of each cured layer may be 20 μm to 100 μm, and the curing time of each layer may be 4s to 8 s. The soaking time of the alcohol is preferably 3min to 5 min. The wavelength of the ultraviolet light for post-processing the formed piece is in the light wave band which can be sensed by the photoinitiator, and the post-processing time is 15-20 min.
Specifically, the method comprises the following steps:
s11 the prepared resin is slowly poured into a resin tank of a photocurable 3D printing apparatus, a three-dimensional CAD model is introduced into the apparatus to mold the resin, and after the molding, the molded article is immersed in alcohol to clean the resin remaining on the surface of the molded article. The alcohol soaking time is 3 min-5 min; the 3D printing technology adopts ultraviolet light curing equipment or digital light processing equipment; wherein the laser scanning speed of the ultraviolet curing equipment is 500-1000 mm/s; the digital light processing equipment carries out layered curing on the photosensitive resin, the thickness of each layer of curing is 20-100 mu m, and the curing time of each layer is 4-8 s.
S12 the molded article is further exposed to light in the ultraviolet curing lamp box to cure the uncured resin inside the molded article. Wherein the wavelength range of ultraviolet light is within the wavelength range of light which can be sensed by the photoinitiator, and the irradiation time of the ultraviolet light is 15-20 min.
As shown in fig. 1 to 4, the present invention provides a driving method of driving a photosensitive resin molded article having a shape memory function, the method comprising the steps of:
s21, increasing the temperature of the photosensitive resin forming piece in the initial shape to T1, wherein T1 is larger than the glass transition temperature Tg of the photosensitive resin forming piece, and applying external force to the photosensitive resin forming piece in the initial shape to deform the photosensitive resin forming piece in the initial shape to obtain a temporary-shaped photosensitive resin forming piece;
s22, keeping the applied external force unchanged, lowering the temperature of the temporary shaped photosensitive resin molded article to T2, wherein T2 is less than the glass transition temperature Tg of the photosensitive resin molded article, fixing the temporary shaped photosensitive resin molded article, and removing the external force;
s23 raises the temperature to T1 again, returning the temporarily shaped photosensitive resin molded article to the original shape.
Heating in step S21 and step S23 by a water bath method, and cooling in step S22 by the water bath method; preferably, T1 is Tg +10 ℃ to Tg +30 ℃ and T2 is Tg-10 ℃ to Tg-30 ℃.
Specifically, the method for driving the photosensitive resin molded article includes the steps of:
s31, the formed piece is the initial shape of SMP, the glass transition temperature Tg of the formed piece is measured, the temperature of the formed initial shape is raised to T1(T1 > Tg), and external force is applied to deform the formed initial shape within the elastic limit to obtain a temporary shape;
s32, keeping the applied external force unchanged, reducing the temperature of the temporary shape SMP to T2, wherein T2 is less than the glass transition temperature Tg of the SMP, fixing the deformation of the SMP and removing the external force;
s33 the temperature is again raised to T1 and the SMP reverts to the original shape.
The temperature change in the above steps S31, S32, S33 may be realized by water baths of different temperatures. T1 is preferably Tg +10 ℃ to 30 ℃ and T2 is preferably Tg-10 ℃ to 30 ℃.
The shape memory property of the formed article can be roughly evaluated by the above-described procedure in said step S31: in the S32 process, after the external force is removed, the deformation hardly changes, which indicates that the formed piece has excellent shape fixing rate; the shape recovered in the S33 process is consistent with the initial shape of the formed part, which indicates that the formed part has excellent shape recovery rate; by recording the time of the S32 process, the rate of shape recovery can be reflected.
Example 1
(1) The preparation method comprises the following steps of selecting 90g of tert-butyl acrylate as a monomer of a photosensitive resin, 10g of 1, 6-hexanediol diacrylate as a cross-linking agent of the photosensitive resin, and 1g of bis (2,4, 6-trimethylbenzoyl) phosphine oxide as a photoinitiator. Mixing the three materials, and performing ultrasonic treatment for 10min until colorless transparent liquid is formed.
(2) Slowly pouring the prepared photosensitive resin into a resin tank of a light curing device, introducing a three-dimensional CAD model, namely a ring with a gap into a DLP device, forming the ring as shown in figure 3, setting the forming parameters to be 20 mu m thick for each curing layer and 5s for each curing layer, and soaking the formed piece with alcohol for 5min after forming so as to clean the residual resin on the surface of the formed piece;
(3) and (3) post-processing of a formed piece: the molded article was further exposed to light in an ultraviolet curing lamp for 20min to cure the uncured photosensitive resin inside the molded article. The above preparation and forming process is shown in fig. 2.
(4) Heating the formed initial shape ring to T1 ═ Tg +20 ℃, applying an external force to deform it into an elongated temporary shape, as shown in fig. 3; keeping the external force unchanged, cooling to a certain temperature T2-Tg-30 ℃, and removing the external force; when the temperature is raised to T1 again, the shape returns from the temporary shape to the original shape, and the driving process is completed, as shown in (a) to (g) of fig. 4.
Example 2
(1) 80g of isobornyl acrylate is selected as a monomer of the photosensitive resin, 20g of 1, 6-hexanediol dimethacrylate is selected as a cross-linking agent of the photosensitive resin, and 1g of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide is selected as a photoinitiator. Mixing the three materials together, and performing ultrasonic treatment for 10min until colorless transparent liquid is formed to obtain photosensitive resin.
(2) Slowly pouring the prepared photosensitive resin into a resin tank of a light curing device, introducing a three-dimensional CAD model into a DLP device to form, setting the forming parameters to be 50 mu m thick for each curing layer, setting the curing time of each layer to be 8s, and soaking the formed piece for 5min by using alcohol after forming so as to clean the residual photosensitive resin on the surface of the formed piece;
(3) and (3) post-processing of a formed piece: the molded article was further exposed to light in an ultraviolet curing lamp for 20min to cure the uncured photosensitive resin inside the molded article.
(4) Heating the formed initial shape ring to T1-Tg +30 ℃, and applying external force to deform the ring into a long temporary shape; keeping the external force unchanged, cooling to a certain temperature T2-Tg-10 ℃, and removing the external force; when the temperature is raised to T1 again, the shape is returned to the original shape from the temporary shape, and the driving process is completed.
Example 3
(1) Selecting 70g of acrylic acid-beta-hydroxyethyl ester as a monomer of photosensitive resin, 30g of polyethylene glycol dimethacrylate as a cross-linking agent of the photosensitive resin, and 1g of alpha, alpha-diethoxyacetophenone as a photoinitiator. Mixing the three materials, and performing ultrasonic treatment for 10min until colorless transparent liquid is formed.
(2) Slowly pouring the prepared photosensitive resin into a resin tank of a light curing device, introducing a three-dimensional CAD model into a DLP device to form, setting the forming parameters to be 100 mu m thick for each curing layer, setting the curing time of each layer to be 8s, and soaking the formed piece for 5min by using alcohol after forming so as to clean the residual photosensitive resin on the surface of the formed piece;
(3) and (3) post-processing of a formed piece: the molded article was further exposed to light in an ultraviolet curing lamp for 18min to cure the uncured photosensitive resin inside the molded article.
(4) Heating the formed initial shape ring to T1-Tg +20 ℃, and applying external force to deform the ring into a long temporary shape; keeping the external force unchanged, cooling to a certain temperature T2-Tg-20 ℃, and removing the external force; when the temperature is raised to T1 again, the shape is returned to the original shape from the temporary shape, and the driving process is completed.
Example 4
(1) 60g of isobornyl acrylate is selected as a monomer of photosensitive resin, 40g of polyethylene glycol dimethacrylate is selected as a cross-linking agent of the photosensitive resin, and 1.5g of alpha, alpha-dimethoxy-alpha-phenylacetophenone is selected as a photoinitiator. Mixing the three materials, and performing ultrasonic treatment for 10min until colorless transparent liquid is formed.
(2) Slowly pouring the prepared photosensitive resin into a resin tank of photocuring equipment, introducing a three-dimensional CAD model into SLA equipment to form the photosensitive resin, setting the forming parameter to be 800mm/s, and soaking the formed piece for 5min by using alcohol after forming so as to clean the residual photosensitive resin on the surface of the formed piece;
(3) and (3) post-processing of a formed piece: the molded article was further exposed to light in an ultraviolet curing lamp for 20min to cure the uncured photosensitive resin inside the molded article.
(4) Heating the formed initial shape ring to T1 ═ Tg +10 ℃, and applying external force to deform the ring into a long temporary shape; keeping the external force unchanged, cooling to a certain temperature T2-Tg-20 ℃, and removing the external force; when the temperature is raised to T1 again, the shape is returned to the original shape from the temporary shape, and the driving process is completed.
Example 5
(1) Selecting 50g of tert-butyl acrylate as a monomer of photosensitive resin, 50g of 1, 6-hexanediol diacrylate as a cross-linking agent of the photosensitive resin, and 2g of alpha, alpha-dimethoxy-alpha-phenylacetophenone as a photoinitiator. Mixing the three materials, and performing ultrasonic treatment for 8min until colorless transparent liquid is formed.
(2) Slowly pouring the prepared photosensitive resin into a resin tank of photocuring equipment, introducing a three-dimensional CAD model into SLA equipment to form the photosensitive resin, setting the forming parameter to be 900mm/s, and soaking the formed piece for 5min by using alcohol after forming so as to clean the residual photosensitive resin on the surface of the formed piece;
(3) and (3) post-processing of a formed piece: the molded article was further exposed to light in an ultraviolet curing lamp for 15min to cure the uncured photosensitive resin inside the molded article.
(4) Heating the formed initial shape ring to T1 ═ Tg +10 ℃, and applying external force to deform the ring into a long temporary shape; keeping the external force unchanged, cooling to a certain temperature T2-Tg-30 ℃, and removing the external force; when the temperature is raised to T1 again, the shape is returned to the original shape from the temporary shape, and the driving process is completed.
In the above embodiments, the initial shape is deformed into a temporary shape by applying an external force, which should be within the elastic limit of the forming member, and the temporary shape can be designed artificially by the external force according to the actual application requirement.
Fig. 5 shows the change rule of the shape fixing rate of the molded article with different cross-linking agent contents of the photosensitive resin system in example 1 with the cycle number, and it can be seen that the 4D printed molded article of the photosensitive resin system in example 1 has excellent shape fixing rate, especially when the content of the cross-linking agent is low, the cycle number that the 4D printed molded article can undergo is large, and the shape fixing rate as high as about 97% can be obtained.
FIG. 6 shows the change of the shape recovery rate with cycle number of the molded article with different cross-linking agent contents of the photosensitive resin system in example 1, and it can be seen that the 4D printed molded article with the photosensitive resin system in example 1 has excellent shape recovery rate, and when the content of the cross-linking agent is low, the shape recovery rate is higher. At a crosslinker content of 10% and after 14 cycles of "deformation-recovery", the shape recovery is as high as 100%, i.e. the shape can be completely recovered.
FIG. 7 is a graph showing the relationship between the content of the crosslinking agent and the shape recovery time in example 1, and it can be seen that the recovery time is in the range of 7s to 13s, and the smaller the recovery time, the faster the recovery rate is indicated, further showing that the 4D printed molded article obtained in example 1 has a higher shape recovery rate.
The shape memory properties of the shaped article can be roughly evaluated by the above procedure: the deformation of the temporary shape hardly changes after the external force is removed, which indicates that the formed piece has excellent shape fixing rate; the shape obtained after recovery is consistent with the initial shape of the formed part, which indicates that the formed part has excellent shape recovery rate; by recording the time of the recovery process, the rate of shape recovery can be reflected.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (6)

1. A photosensitive resin preparation, forming and driving method for 4D printing is characterized by comprising the following steps:
s1, adding a multifunctional acrylate cross-linking agent into a monofunctional acrylate monomer, and then adding a photoinitiator to obtain a mixture; subjecting the mixture to ultrasonic treatment until a colorless and transparent liquid is formed, so as to obtain a photosensitive resin for 4D printing;
the monofunctional acrylate monomer is any one or more of tert-butyl acrylate, beta-hydroxyethyl acrylate and isobornyl acrylate; the multifunctional acrylate is any one or more of 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, polyethylene glycol diacrylate and polyethylene glycol dimethacrylate;
the photoinitiator is a free radical type photoinitiator, and the free radical type photoinitiator is any one or more of bis (2,4, 6-trimethylbenzoyl) phosphine oxide, bis (2, 6-dimethoxybenzoyl) - (4',4' -dimethyloctyl-2) phosphine oxide, alpha-diethoxyacetophenone and alpha, alpha-dimethoxy-alpha-phenylacetophenone;
s2, printing and forming the photosensitive resin prepared in the S1 by using a photocuring printing device to obtain a formed piece, and cleaning the residual photosensitive resin on the surface of the formed piece; irradiating the formed piece with ultraviolet light to completely cure the formed piece, thereby obtaining a photosensitive resin formed piece with a shape memory function;
the photocuring printing equipment is ultraviolet photocuring equipment or digital light processing equipment, wherein the laser scanning rate of the ultraviolet photocuring equipment is 500-1000 mm/s; the digital light processing equipment carries out layered curing on the photosensitive resin, the thickness of each layer of curing is 20-100 mu m, and the curing time of each layer is 4-8 s;
s3, driving the photosensitive resin molded article prepared in S2, specifically including:
s31, increasing the temperature of the photosensitive resin forming piece in the initial shape to T1, wherein T1 is larger than the glass transition temperature Tg of the photosensitive resin forming piece, and applying external force to the photosensitive resin forming piece in the initial shape to deform the photosensitive resin forming piece in the initial shape to obtain a temporary-shaped photosensitive resin forming piece;
s32, keeping the applied external force unchanged, lowering the temperature of the temporary shaped photosensitive resin molded article to T2, wherein T2 is less than the glass transition temperature Tg of the photosensitive resin molded article, fixing the temporary shaped photosensitive resin molded article, and removing the external force;
s33 raises the temperature to T1 again, returning the temporarily shaped photosensitive resin molded article to the original shape.
2. The method according to claim 1, wherein in step S1, the mass fraction ratio of the monofunctional acrylate monomer to the multifunctional acrylate crosslinking agent is 1:1 to 9:1, and the mass of the photoinitiator is 0.5 to 2% of the total mass of the monofunctional acrylate monomer and the multifunctional acrylate crosslinking agent.
3. The method according to claim 1, wherein the time of the ultrasonic treatment is 5min to 10 min.
4. The method according to claim 1, wherein in step S2, the photosensitive resin remaining on the surface of the formed article is cleaned by an alcohol immersion method, wherein the alcohol immersion time is 3min to 5 min; the wavelength of the ultraviolet light is within the wavelength range of the light which can be sensed by the photoinitiator, and the irradiation time of the ultraviolet light is 15-20 min.
5. The method of claim 1, wherein the temperature is raised in step S31 and step S33 by a water bath method, and the temperature is lowered in step S32 by a water bath method; t1 is Tg + 10-Tg +30 ℃ and T2 is Tg-10-Tg-30 ℃.
6. The method according to claim 1, wherein the external force is within an elastic limit of the photosensitive resin molded article in step S31.
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